CN105514413A - Lithium ion anode and cathode materials atmosphere immersive sintering process and related sintering device - Google Patents
Lithium ion anode and cathode materials atmosphere immersive sintering process and related sintering device Download PDFInfo
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- CN105514413A CN105514413A CN201511006860.7A CN201511006860A CN105514413A CN 105514413 A CN105514413 A CN 105514413A CN 201511006860 A CN201511006860 A CN 201511006860A CN 105514413 A CN105514413 A CN 105514413A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a technique process and an operation method for realizing immersive sintering of lithium ion anode and cathode materials with reaction atmosphere or reaction gas. The sintering process is suitable for a synthetic reaction under specific atmosphere, an oxidizing reaction requiring an oxygen atmosphere, a carbon cladding reaction under organic gas, and a quenching reaction requiring fast cooling of cooling gas; the defect that conventional sintering gas floats at the surface of the material is solved by whole course gas immersive sintering manner, thus greatly improving the reaction activity when the gas serves as a reaction raw material and inertia protection when the gas serves as a protection atmosphere, being favorable for meeting the preparing of lithium battery anode and cathode materials requiring the gas to participate the reaction or provide the protection atmosphere, and realizing the immersive sintering process under the gas atmosphere by particle size screening after precursor pelleting, oppositely buckling upper and lower symmetric expanded panels of an immersive sintering furnace and a smart design of the expanded panel and a venting tower.
Description
Technical field
The atmosphere that the present invention relates to a kind of lithium ion positive and negative pole material soaks into formula sintering process and relevant agglomerating plant.
Background technology
Universal along with new-energy automobile and the various vehicles, new forms of energy lithium battery is proud to be applied widely, lithium ion battery plus-negative plate material synthesis and quality assurance seem particularly important; Lithium ion positive and negative pole material is subordinate to the category of powder body material, high temperature sintering is the conventional process process of materials synthesis, high temperature sintering is conducive to the crystalline state formation of various material and growing up and controlling of crystal grain, and therefore sintering furnace is widely used in the various fields of new energy materials processing synthesis.
Mostly the process of sintering is the powder mixed or solid material to be heated in suitable environment or atmosphere, by series of physical and chemical change, particle is made to occur to melt a series of changes such as decomposition, then merge in the temperature province of specifying, obtain the effect that various physical property, chemical property and chemical property obtain index request.The resistance-type tubular type heat-agglomerating stove that the sintering furnace adopted both at home and abroad is at present mainly traditional and frame Muffle furnace.
Traditional heat-agglomerating stove comprises body of heater shell, heat-insulation layer, calandria and burner hearth etc., and when electric current is by calandria, the Electrical resistance produces heat had by calandria itself, utilizes radiation and the conduction of heater heat, is sintered solid material in heating furnace.For avoiding thermal loss, between burner hearth and body of heater shell, there is very thick heat-insulation layer, to ensure that heat concentrates on burner hearth inside.This design can holding temperature within the specific limits stable, but cannot meet another key factor of sintering---the requirement of atmosphere.When gas synthesizes various lithium ion positive and negative pole material as reaction raw material, usually " can only make only a cursory investigation of some situation " on the surface of material, fully cannot contact with the particle of material, thus after current conventional lithium ion positive and negative pole material is sintered, upper and lower surface difference is large, material quality and poor stability; Such as: the nitrogen atmosphere in LiFePO 4 material sintering process have impact on the content of ferric iron impurity in product, oxygen atmosphere valence stability determining finished-product material in the synthesis of nickel-cobalt lithium manganate material sintering etc.In addition, mostly powder body material is to load with the vessel such as crucible, porcelain boat in sintering process, and whether great or small how this vessel, exist the wall of certain altitude more, this is to the contact area hindering atmosphere and powder body material, reduces protective effect or the reactivity of atmosphere; Seriously govern the stable of material quality and output increased, thus probe into a kind of that can realize the synthesis of lithium ion positive and negative pole material " soak into formula " with atmosphere and contact the technology sintered seem especially important.
Summary of the invention
The present invention is directed to conventional lithium ion positive and negative pole material sintering stability poor; specific gas requires or atmosphere fully cannot contact with material; reduce protective effect or the reactivity of atmosphere, propose a kind of lithium ion positive and negative pole material and reaction atmosphere or reacting gas of realizing and soak into the technical matters and method of operation that formula sinters:
The atmosphere that the invention provides a kind of lithium ion positive and negative pole material soaks into formula sintering process and relevant agglomerating plant, and it is characterized in that, concrete technology is as follows:
(1) presoma granulation screening: the precursor mixture mixed of lithium ion positive and negative pole material is added granulation balling-up in balling machine, then screening obtains the good particle precursor material of consistency, finally will obtain product precursor mixture, before sintering material is laid on the concavo-convex extended surface plate alternately presented, waits to be sintered;
(2) heat treatment contact-making surface is expanded: formula sintering furnace will be soaked into and open, take out the symmetrical extended surface plate fastened up and down, be laid on lower extended surface plate by the mixed material of specific positive and negative pole material after mixing, material thickness was advisable just not have equally distributed ventilative column overhead on lower extended surface plate; The lower expansion panels in alignment of upper extended surface plate and cloth full with substance is fastened, in guarantee, extended surface plate is placed with lower extended surface plate is concentric, upper expansion panel radius comparatively descends the width of little 1 the ventilative tower of extended surface plate, in the peripheral circumferential of lower extended surface plate, quartering punishment is furnished with four bolt noses, for passing in and out lifting operation during spheroid burner hearth; The extended surface plate utilizing three-wire hook to sling to have fastened up and down, slowly put into spheroid burner hearth, placement on the table top formed is shunk stable in lower hemisphere, then first body of heater soaking into formula sintering furnace is fastened, what first sintering furnace was fitted together perfectly fastens with bottom frit body of heater, and between body of heater, outer occlusion material is aluminum alloy material coupling silicagel pad structure;
(3) formula sintering is soaked under particular atmosphere: open air intake valve on the upside of body of heater, adjusting gas flow, pre-aeration body, after a period of time, in gas outlet place checking body of heater, whether gas is full of, and after gas is full of, opens the temperature controller of body of heater simultaneously, thermocouple is in the middle part of body of heater, temperature in Real-Time Monitoring body of heater; Heat up according to the preset temperature curve of certain material and sinter, the gentle uninterrupted of air inlet type is regulated in the specific stage of reaction, gas enters upper hemisphere burner hearth through dispersion sphere, under air inlet gas pressure promotes, gas is through there being upper extended surface plate, and---mixed material---lower extended surface plate---lower hemisphere burner hearth, discharges finally by by outlet pipe.
The predecessor of the lithium ion battery plus-negative plate material described in step (1) is through the also unified screening of balling machine granulating and forming, and wherein screening mesh sieve aperture number is 100-200 order.
Described soaks into formula sintering furnace thoroughly, described burner hearth is spherical burner hearth, sintering furnace body comprise hinged upper strata body of heater, lower floor's body of heater and up and down extended surface plate form soak into sintering zone, upper strata body of heater is provided with air inlet, diffusion sphere, air inlet connects external feed stream pipe, external feed stream pipeline is provided with flowmeter, Pressure gauge, and external pipe is directly connected to gas supply device; Road lower floor body of heater is with gas outlet, and gas outlet is connected with outlet pipe, and outlet pipe has valve.
Described soaks into formula sintering furnace, the air-vent of described dispersion spherical face is uniformly distributed, dispersion sphere is the round sphere structure of one and body of heater concentric, the edge of dispersion sphere and the angled A in the body of heater center of circle, cone angle A is 10-30 °, and diffusion disc axis is positioned at vertical direction and through burner hearth center.
Described soaks into formula sintering furnace, what the described plate of extended surface was up and down formed soak into, and sintering zone fastens mutually by upper and lower extended surface plate forms, upper and lower extended surface plate surface distributed has multiple ventilative tower, the ventilative Deethanizer design of extended surface plate, greatly add the contact area of plane support board and material, monomer is breathed freely with multiple air vent hole on tower, and air vent hole runs through extended surface plate, and extended surface sheet material matter is corundum structure; Upper strata extended surface plate expands the width of the little ventilative tower of panel radius compared with lower floor, the ventilative tower hole diameter of lower extended surface plate is 0.1-1mm, the vent diameter of upper extended surface plate is more bigger than lower vent diameter, at 0.5-2mm, in the peripheral circumferential of lower extended surface plate, quartering punishment is furnished with four bolt noses, for passing in and out lifting operation during spheroid burner hearth.
Described soaks into formula sintering furnace, and described lower floor's bottom of furnace body is provided with gas outlet, and gas outlet connects outside outlet pipe, and outside outlet pipe is provided with control valve.
Described soaks into formula sintering process thoroughly, is applicable to the synthetic reaction under needs protective atmosphere, the quenching reaction needing the oxidation reaction of oxygen atmosphere and need refrigerating gas to cool fast.
Described pre-logical gas corresponding to calcined materials is react corresponding protective gas or reacting gas with positive and negative pole material; nickle cobalt lithium manganate synthesizes the gas that corresponding oxygen is synthetic reaction; LiFePO 4 material synthesizes and in lithium titanate building-up process, corresponding acetylene and propylene are carbon-source gas, and nitrogen is protective gas.
The invention has the advantages that:
1, the gas of lithium ion positive and negative pole material soaks into formula sintering process, and for reaction solid material and gas provide sufficient contact area and chance, gas penetrates up and down through air inlet, the material of extended surface plate, is finally discharged by gas outlet; The Flow-rate adjustment of admission line can realize the atmosphere requirements under different preset temperature section condition, and essential scope temperature section increases air inflow, stablize conversion zone and balances air inflow; Pressure regulates the pressure that can regulate and control in the spheroid burner hearth of top, thus control gas penetrates the velocity of liquid assets in process at material, and under realizing hot conditions, material " soaking into " under particular atmosphere sinters;
2, the design of agglomerating plant: chamber structure, solves the Dead Core Problems of conventional sintering stove, and adds sintering furnace air-tightness, and under being more conducive to sintering condition, all even of atmosphere is stablized; Dispersion sphere: by the dispersion sphere increased inside air inlet, avoid and enter the drawback that gas reduces local temperature in body of heater, the gas of air inlet is not directly contacted with material, avoid the temperature gradient change directly entering and cause, disperse the spherical design of sphere to be conducive to gas diffusion in body of heater and the eliminating of foreign gas simultaneously; Extended surface plate: the even design being distributed with extended surface plate solves top-down gas permeability problem on the one hand, and tight can not trickle down material again in the base plane of flat board simultaneously, ensure that the formula of soaking into that material is attached on concavo-convex extended surface plate sinters; The circuit design of upper entering and lower leaving and the control of flow and pressure of pipeline: be conducive on the one hand ensureing that top contacts atmosphere with material, be conducive to the anti-suck sintering gas on the other hand, lower chamber also serves the effect of buffering.
Accompanying drawing explanation
Fig. 1 conventional solid synthesizing iron lithium phosphate SEM schemes;
Fig. 2 embodiment 2 gained LiFePO4 SEM schemes;
The circulation of Fig. 3 embodiment 1 gained nickle cobalt lithium manganate and conventional nickel-cobalt lithium manganate material circulation comparison diagram;
Fig. 4 is the profile that the present invention relates to agglomerating plant;
Fig. 5 is the state diagram after lower extended surface plate cloth;
Fig. 6 be upper and lower extended surface plate cloth and fasten after state diagram.
In accompanying drawing: 1, burner hearth; 2, air inlet; 3, gas outlet; 4, sphere is disperseed; 5, corundum plate; 6, ventilative tower; 7, hinge; 8, air vent hole; 9, bolt nose.
Embodiment
During the invention process, by the nodularization granulation of the predecessor to lithium ion positive and negative pole material, the distribution of material of the large small particle diameter of screening 100-200 mesh sieve, obtains maximum pine dress gap; Utilize simultaneously and soak into formula sintering furnace structural design, mixing is obtained product precursor mixture, before sintering material is laid on the concavo-convex extended surface plate alternately presented.To soak into formula sintering furnace to open, and take out the symmetrical extended surface plate fastened up and down, and be laid on lower extended surface plate by the mixed material of specific positive and negative pole material after mixing, material thickness was advisable just not have equally distributed ventilative column overhead on lower extended surface plate;
Relatively fastened by laterally zygomorphic extended surface plate, keep level, the plate of extended surface up and down that simultaneously structure is consistent increases the contact area of material and extended surface plate, make material be present in extended surface plate breathe freely tower gap between, and ensure that upper extended surface plate is placed with lower extended surface plate is concentric, upper expansion panel radius comparatively descends the width of little 1 the ventilative tower of extended surface plate, the ventilative tower hole diameter of lower extended surface plate is 0.1-1mm, the vent diameter of upper extended surface plate is more bigger than lower vent diameter, at 0.5-2mm, in the peripheral circumferential utilizing three-wire hook to hang up lower extended surface plate, quartering punishment is furnished with four bolt noses, slowly the plate of extended surface up and down fastened is put into spheroid burner hearth, placement on the table top formed is shunk stable in lower hemisphere, then first body of heater soaking into formula sintering furnace is fastened, what first sintering furnace was fitted together perfectly fastens with bottom frit body of heater, between body of heater, outer occlusion material is aluminum alloy material coupling silicagel pad structure,
Open air intake valve on the upside of body of heater, adjusting gas flow, pre-aeration body, after a period of time, in gas outlet place checking body of heater, whether gas is full of, after gas is full of, open the temperature controller of body of heater, thermocouple is in the middle part of body of heater simultaneously, temperature in Real-Time Monitoring body of heater; Heat up according to the preset temperature curve of certain material and sinter, in specific stage of reaction adjusting air inflow quantity size, gas enters upper hemisphere burner hearth through dispersion sphere, under air inlet gas pressure promotes, gas is through there being upper extended surface plate---mixed material---lower extended surface plate---lower hemisphere burner hearth, discharge finally by by outlet pipe, can be controlled by the atmosphere pressures regulating give vent to anger size and charge flow rate to realize in first body of heater in sintering process; Terminate rear replaceable air inlet gas supply type, realize Buchholz protection during cooling, until material cooling.
Embodiment 1
The soak into formula of nickel-cobalt lithium manganate material under oxygen atmosphere sinters:
The precursor mixture of nickel hydroxide cobalt manganese, lithium carbonate material is added in balling machine, granulation balling-up, then utilize screen cloth 100-200 to screen and obtain the good particle precursor material of consistency, finally will obtain product precursor mixture, formula sintering furnace will be soaked into open, the sphere cavity of to be radius be on sintering furnace top 18cm radius, the sphere cavity of the latter half to be radius be 21cm radius; Take out the symmetrical extended surface plate fastened up and down, take off extended surface plate, by the nickel hydroxide cobalt manganese of nickel-cobalt lithium manganate material and the mixture of lithium carbonate, be laid on the concavo-convex extended surface plate alternately presented, the thickness controlling material is even, and material surface maintains an equal level with ventilative tower upper surface;
Relatively fastened by laterally zygomorphic extended surface plate, keep level, the plate of extended surface up and down that simultaneously structure is consistent increases the contact area of material and extended surface plate, make material be present in extended surface plate breathe freely tower gap between, and ensure that upper extended surface plate is placed with lower extended surface plate is concentric, upper expansion panel radius comparatively descends the width of little 1 the ventilative tower of extended surface plate, the ventilative tower hole diameter of lower extended surface plate is 1mm, the vent diameter of upper extended surface plate is more bigger than lower vent diameter, at 2mm, in the peripheral circumferential utilizing three-wire hook to hang up lower extended surface plate, quartering punishment is furnished with four bolt noses, slowly the plate of extended surface up and down fastened is put into spheroid burner hearth, placement on the table top formed is shunk stable in lower hemisphere, then first body of heater soaking into formula sintering furnace is fastened, what first sintering furnace was fitted together perfectly fastens with bottom frit body of heater, between body of heater, outer occlusion material is aluminum alloy material coupling silicagel pad structure,
Open air intake valve on the upside of body of heater, adjustment oxygen flow is the flow pre-aeration body (gas flow is the flow rate calculation being full of actual sphere cavity volume according to 10min) of 3L/min, after 15min, in gas outlet place checking body of heater, whether gas is full of, after gas is full of, open the temperature controller of body of heater simultaneously, be in the thermocouple in the middle part of body of heater, temperature in Real-Time Monitoring body of heater; Carry out intensifications sintering according to the temperature curve 375 DEG C-2h+550 DEG C-6h+800 DEG C of-10h preset, in 0-375 DEG C of temperature section, hydroxyl accelerated decomposition, adjusting gas flow 2L/min, standard-sized sheet is given vent to anger valve, acceleration produce the discharge of steam; In 375-550 DEG C of temperature section, reaction raw materials lithium carbonate starts to decompose generation carbon dioxide, stage of reaction adjusting air inflow quantity size is 1L/min, foreign gas under the promotion newly entering oxygen atmosphere,---lower extended surface plate---lower hemisphere burner hearth from top to bottom, through mixed material, directly discharge via outlet pipe, avoid the interference effect because of impurity atmosphere, improve exposure level and the reactivity of mixed material and reaction gas powder oxygen, greatly improve the stability of materials synthesis; 550-800 DEG C of temperature section is soaking zone, the oxygen supply continued ensure that material is fully oxidized, after sintering terminates, first strengthen oxygen quantity delivered 3L/min, utilize recent gas flow, improve temperature-fall period pressure and rate of temperature fall, prevent the oxygen phenomenon of analysing in conventional nickle cobalt lithium manganate building-up process to occur, greatly protect material quality; When temperature is reduced to below 400 DEG C, turn down air inflow 0.5L/min until material cools completely, obtain LiFePO4 finished-product material.
Embodiment 2
LiFePO 4 material formula of soaking in a nitrogen atmosphere sinters:
The precursor mixture of ferric phosphate, lithium carbonate material is added in balling machine, granulation balling-up, then utilize screen cloth 100-200 to screen and obtain the good particle precursor material of consistency, finally will obtain product precursor mixture, gas powder is soaked into formula sintering furnace open, the sphere cavity of to be radius be on sintering furnace top 18cm radius, the sphere cavity of the latter half to be radius be 21cm radius; Take out the symmetrical extended surface plate fastened up and down, take off extended surface plate, by the mixture of the ferric phosphate of LiFePO 4 material, glucose and lithium carbonate, be laid on the concavo-convex extended surface plate alternately presented, the thickness controlling material is even, and material surface maintains an equal level with ventilative tower upper surface;
Relatively fastened by laterally zygomorphic extended surface plate, keep level, the plate of extended surface up and down that simultaneously structure is consistent increases the contact area of material and extended surface plate, make material be present in extended surface plate breathe freely tower gap between, and ensure that upper extended surface plate is placed with lower extended surface plate is concentric, upper expansion panel radius comparatively descends the width of little 1 the ventilative tower of extended surface plate, the ventilative tower hole diameter of lower extended surface plate is 0.3mm, the vent diameter of upper extended surface plate is more bigger than lower vent diameter, at 2mm, in the peripheral circumferential utilizing three-wire hook to hang up lower extended surface plate, quartering punishment is furnished with four bolt noses, slowly the plate of extended surface up and down fastened is put into spheroid burner hearth, placement on the table top formed is shunk stable in lower hemisphere, then first body of heater soaking into formula sintering furnace is fastened, what first sintering furnace was fitted together perfectly fastens with bottom frit body of heater, between body of heater, outer occlusion material is aluminum alloy material coupling silicagel pad structure,
Open air intake valve on the upside of body of heater, adjustment oxygen flow is the flow logical nitrogen (gas flow is the flow rate calculation being full of actual sphere cavity volume according to 10min) in advance of 3L/min, after 15min, in gas outlet place checking body of heater, whether gas is full of, after gas is full of, open the temperature controller of body of heater simultaneously, be in the thermocouple in the middle part of body of heater, temperature in Real-Time Monitoring body of heater; Intensification sintering is carried out according to the temperature curve 350 DEG C of-2h+720 DEG C of-6h preset, in 0-350 DEG C of temperature section, glucose fast decoupled, produce a large amount of carbon dioxides and steam, adjusting gas flow 2L/min, standard-sized sheet is given vent to anger valve, accelerate produce the discharge of steam and carbon dioxide; In 350-550 DEG C of warming temperature section, the carbon that reaction raw materials breakdown of glucose produces starts reduction occurs, this temperature section starts crystallization simultaneously, be applicable to the coated process of carbon, it is 0.5L/min that this temperature section reduces gas flow, but mix the acetylene gas of 1:1, the reduction reaction of ferric phosphate and carbon source and carbon coating reaction are fully carried out; In 550-720 DEG C of warming temperature section, reaction raw materials lithium carbonate decomposes the more carbon dioxide of generation, and adjusting air inflow quantity size is 1L/min, and foreign gas is Accelerating Removal under the promotion newly entering oxygen atmosphere; In whole course of reaction, nitrogen from top to bottom,---lower extended surface plate---lower hemisphere burner hearth through mixed material, directly discharge via outlet pipe, by the control of flow and the adjustment of valve of giving vent to anger, avoid the interference effect because of impurity atmosphere, also ensure that fully carrying out of carbon source reduction reaction simultaneously, put forward the stability greatly improving materials synthesis; After sintering terminates, strengthen nitrogen gas supply amount 3L/min, realize the fast cooling of material under nitrogen atmosphere protection; when temperature is reduced to below 200 DEG C, turn down air inflow 0.5L/min, prevent material to be oxidized; until material cools completely, obtain LiFePO4 finished-product material.
Embodiment 3
The coated lithium titanate anode material of carbon formula of soaking in a nitrogen atmosphere sinters:
The precursor mixture of titanium dioxide, lithium carbonate material is added in balling machine, granulation balling-up, then utilize screen cloth 100-200 to screen and obtain the good particle precursor material of consistency, finally will obtain product precursor mixture, gas powder is soaked into formula sintering furnace open, the sphere cavity of to be radius be on sintering furnace top 18cm radius, the sphere cavity of the latter half to be radius be 21cm radius; Take out the symmetrical extended surface plate fastened up and down, take off extended surface plate, by the mixture of the oxide spinel lithium of negative material, the composition of titanium dioxide, be laid on the concavo-convex extended surface plate alternately presented, the thickness controlling material is even, and material surface maintains an equal level with ventilative tower upper surface;
Relatively fastened by laterally zygomorphic extended surface plate, keep level, the plate of extended surface up and down that simultaneously structure is consistent increases the contact area of material and extended surface plate, make material be present in extended surface plate breathe freely tower gap between, and ensure that upper extended surface plate is placed with lower extended surface plate is concentric, upper expansion panel radius comparatively descends the width of little 1 the ventilative tower of extended surface plate, the ventilative tower hole diameter of lower extended surface plate is 0.3mm, the vent diameter of upper extended surface plate is more bigger than lower vent diameter, at 2mm, in the peripheral circumferential utilizing three-wire hook to hang up lower extended surface plate, quartering punishment is furnished with four bolt noses, slowly the plate of extended surface up and down fastened is put into spheroid burner hearth, placement on the table top formed is shunk stable in lower hemisphere, then first body of heater soaking into formula sintering furnace is fastened, what first sintering furnace was fitted together perfectly fastens with bottom frit body of heater, between body of heater, outer occlusion material is aluminum alloy material coupling silicagel pad structure,
Open air intake valve on the upside of body of heater, adjust flux is the flow logical nitrogen (gas flow is the flow rate calculation being full of actual sphere cavity volume according to 10min) in advance of 3L/min, after 15min, in gas outlet place checking body of heater, whether gas is full of, after gas is full of, open the temperature controller of body of heater simultaneously, be in the thermocouple in the middle part of body of heater, temperature in Real-Time Monitoring body of heater; Intensification sintering is carried out according to the temperature curve 350 DEG C of-2h+900 DEG C of-12h preset, in 0-350 DEG C of temperature section, in order to discharge carbon dioxide and the steam of reactant output, adjusting gas flow 1L/min, standard-sized sheet is given vent to anger valve, accelerate produce the discharge of steam and carbon dioxide; In 350-650 DEG C of warming temperature section, reaction raw materials lithium carbonate decomposes generating portion carbon dioxide, and lithium carbonate proportion is larger, carbon dioxide volume increases rapidly, it is 2L/min that this temperature section continues to increase gas flow, and keeps outlet pipe standard-sized sheet, and carbon dioxide impurities gas is fully discharged; In 900 DEG C of holding temperature sections, the lithium titanate structure of synthesis progressively tends towards stability, to nitrogen and the propylene mist of its inner logical 1:1, but it provides the environment of propylene carbonization, it is coated that the carbon that propylene gas then decomposes generation progressively realizes material carbon, now need stable and quantitative atmosphere realization response process, therefore this soaking zone reduces nitrogen flow is close give vent to anger valve and air intake valve after 0.2L/min even can pass into a certain amount of gas, regulates throughput to be 0; After sintering terminates; stop propylene gas supply; simple increasing nitrogen gas supply amount 3L/min; realize the fast cooling of material under nitrogen atmosphere protection; when temperature is reduced to below 200 DEG C; air inlet gas can be regulated to be clean compressed air, realizing reducing costs while material cools completely, to obtain LiFePO4 finished-product material.
The conventional phosphoric acid iron lithium material that the LiFePO4 finished-product material that Fig. 2 presents shows compared with Fig. 1, has better dispersiveness.
The nickel-cobalt lithium manganate material that the embodiment 1 shown in Fig. 3 obtains has better cyclicity than conventional nickel-cobalt lithium manganate material; this all changes owing to the formula sintering that soaks into of material in sintering process in atmosphere the drawback that normal sintering gas floats on material surface; greatly improve gas as reactivity during reaction raw materials with as inertia protection during protection atmosphere; the gas that is conducive to satisfying the demand participates in reaction or needs gas to provide the preparation of the lithium ion battery plus-negative plate material of protection atmosphere, has obvious beneficial effect.
Claims (8)
1. the atmosphere that the invention provides a kind of lithium ion positive and negative pole material soaks into formula sintering process and relevant agglomerating plant, and it is characterized in that, concrete technology is as follows:
(1) presoma granulation screening: the precursor mixture mixed of lithium ion positive and negative pole material is added granulation balling-up in balling machine, then screening obtains the good particle precursor material of consistency, finally will obtain product precursor mixture, before sintering material is laid on the concavo-convex extended surface plate alternately presented, waits to be sintered;
(2) heat treatment contact-making surface is expanded: formula sintering furnace will be soaked into and open, take out the symmetrical extended surface plate fastened up and down, be laid on lower extended surface plate by the mixed material of specific positive and negative pole material after mixing, material thickness was advisable just not have equally distributed ventilative column overhead on lower extended surface plate; The lower expansion panels in alignment of upper extended surface plate and cloth full with substance is fastened, in guarantee, extended surface plate is placed with lower extended surface plate is concentric, upper expansion panel radius comparatively descends the width of little 1 the ventilative tower of extended surface plate, in the peripheral circumferential of lower extended surface plate, quartering punishment is furnished with four bolt noses, for passing in and out lifting operation during spheroid burner hearth; The extended surface plate utilizing three-wire hook to sling to have fastened up and down, slowly put into spheroid burner hearth, placement on the table top formed is shunk stable in lower hemisphere, then first body of heater soaking into formula sintering furnace is fastened, what first sintering furnace was fitted together perfectly fastens with bottom frit body of heater, and between body of heater, outer occlusion material is aluminum alloy material coupling silicagel pad structure;
(3) formula sintering is soaked under particular atmosphere: open air intake valve on the upside of body of heater, adjusting gas flow, pre-aeration body, after a period of time, in gas outlet place checking body of heater, whether gas is full of, and after gas is full of, opens the temperature controller of body of heater simultaneously, thermocouple is in the middle part of body of heater, temperature in Real-Time Monitoring body of heater; Heat up according to the preset temperature curve of certain material and sinter, the gentle uninterrupted of air inlet type is regulated in the specific stage of reaction, gas enters upper hemisphere burner hearth through dispersion sphere, under air inlet gas pressure promotes, gas is through there being upper extended surface plate, and---mixed material---lower extended surface plate---lower hemisphere burner hearth, discharges finally by by outlet pipe.
2. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant, it is characterized in that: the predecessor of lithium ion battery plus-negative plate material is through the also unified screening of balling machine granulating and forming, and wherein screening mesh sieve aperture number is 100-200 order.
3. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant, it is characterized in that: described soaks into formula sintering furnace thoroughly, described burner hearth is spherical burner hearth, sintering furnace body comprise hinged upper strata body of heater, lower floor's body of heater and up and down extended surface plate form soak into sintering zone, upper strata body of heater is provided with air inlet, diffusion sphere, air inlet connects external feed stream pipe, external feed stream pipeline is provided with flowmeter, Pressure gauge, and external pipe is directly connected to gas supply device; Road lower floor body of heater is with gas outlet, and gas outlet is connected with outlet pipe, and outlet pipe has valve.
4. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant, it is characterized in that: described soaks into formula sintering furnace, the air-vent of described dispersion spherical face is uniformly distributed, dispersion sphere is the round sphere structure of one and body of heater concentric, the edge of dispersion sphere and the angled A in the body of heater center of circle, cone angle A is 10-30 °, and diffusion disc axis is positioned at vertical direction and through burner hearth center.
5. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant, it is characterized in that: described soaks into formula sintering furnace, what the described plate of extended surface was up and down formed soak into, and sintering zone fastens mutually by upper and lower extended surface plate forms, upper and lower extended surface plate surface distributed has multiple ventilative tower, the ventilative Deethanizer design of extended surface plate, greatly add the contact area of plane support board and material, monomer is breathed freely on tower with multiple air vent hole, air vent hole runs through extended surface plate, and extended surface sheet material matter is corundum structure; Upper strata extended surface plate expands the width of the little ventilative tower of panel radius compared with lower floor, the ventilative tower hole diameter of lower extended surface plate is 0.1-1mm, the vent diameter of upper extended surface plate is more bigger than lower vent diameter, at 0.5-2mm, in the peripheral circumferential of lower extended surface plate, quartering punishment is furnished with four bolt noses, for passing in and out lifting operation during spheroid burner hearth.
6. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant, it is characterized in that: described soaks into formula sintering furnace, described lower floor's bottom of furnace body is provided with gas outlet, gas outlet connects outside outlet pipe, and outside outlet pipe is provided with control valve.
7. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant; it is characterized in that: described soaks into formula sintering process thoroughly; be applicable to the synthetic reaction under needs protective atmosphere, the quenching reaction needing the oxidation reaction of oxygen atmosphere and need refrigerating gas to cool fast.
8. the atmosphere of a kind of lithium ion positive and negative pole material according to claims 1 soaks into formula sintering process and relevant agglomerating plant; it is characterized in that: pre-logical gas corresponding to calcined materials is react corresponding protective gas or reacting gas with positive and negative pole material; nickle cobalt lithium manganate synthesizes the gas that corresponding oxygen is synthetic reaction; LiFePO 4 material synthesizes and in lithium titanate building-up process, corresponding acetylene and propylene are carbon-source gas, and nitrogen is protective gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946555A (en) * | 2017-10-30 | 2018-04-20 | 湖南格兰博智能科技有限责任公司 | The preparation method and lithium ion battery of a kind of lithium titanate anode material |
| CN109585809A (en) * | 2018-11-08 | 2019-04-05 | 山东精工电子科技有限公司 | A kind of shaggy LiFePO 4 material and preparation method thereof |
| CN113120966A (en) * | 2021-03-24 | 2021-07-16 | 安徽博石高科新材料股份有限公司 | Automatic production method of lithium manganate material |
| CN114524471A (en) * | 2022-04-22 | 2022-05-24 | 宜宾锂宝新材料有限公司 | Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202149685U (en) * | 2011-07-06 | 2012-02-22 | 郑州德朗能电池有限公司 | Microwave sintering furnace made of lithium ion battery material |
| JP2014081096A (en) * | 2012-10-15 | 2014-05-08 | Ebara Corp | Vacuum heating furnace |
| CN104110965A (en) * | 2014-07-14 | 2014-10-22 | 洛阳市西格马炉业有限公司 | High-temperature air pressure sintering furnace |
| JP2014214988A (en) * | 2013-04-26 | 2014-11-17 | 東海高熱工業株式会社 | Continuous burning furnace |
| CN104617292A (en) * | 2015-01-20 | 2015-05-13 | 湖南省正源储能材料与器件研究所 | Preparation method of high-capacity spherical Li(Ni, Co, Al)O2 cathode material |
-
2015
- 2015-12-30 CN CN201511006860.7A patent/CN105514413B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202149685U (en) * | 2011-07-06 | 2012-02-22 | 郑州德朗能电池有限公司 | Microwave sintering furnace made of lithium ion battery material |
| JP2014081096A (en) * | 2012-10-15 | 2014-05-08 | Ebara Corp | Vacuum heating furnace |
| JP2014214988A (en) * | 2013-04-26 | 2014-11-17 | 東海高熱工業株式会社 | Continuous burning furnace |
| CN104110965A (en) * | 2014-07-14 | 2014-10-22 | 洛阳市西格马炉业有限公司 | High-temperature air pressure sintering furnace |
| CN104617292A (en) * | 2015-01-20 | 2015-05-13 | 湖南省正源储能材料与器件研究所 | Preparation method of high-capacity spherical Li(Ni, Co, Al)O2 cathode material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107946555A (en) * | 2017-10-30 | 2018-04-20 | 湖南格兰博智能科技有限责任公司 | The preparation method and lithium ion battery of a kind of lithium titanate anode material |
| CN109585809A (en) * | 2018-11-08 | 2019-04-05 | 山东精工电子科技有限公司 | A kind of shaggy LiFePO 4 material and preparation method thereof |
| CN113120966A (en) * | 2021-03-24 | 2021-07-16 | 安徽博石高科新材料股份有限公司 | Automatic production method of lithium manganate material |
| CN114524471A (en) * | 2022-04-22 | 2022-05-24 | 宜宾锂宝新材料有限公司 | Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof |
| CN114524471B (en) * | 2022-04-22 | 2022-07-08 | 宜宾锂宝新材料有限公司 | Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof |
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